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Nickel Catalytic Removal of Alkene Protecting Groups

An olefin-based, nickel-catalyzed technology, which is applied in chemical instruments and methods, catalytic reactions, and the preparation of organic compounds, can solve the problems that palladium metal is expensive and unsuitable for industrial production, and achieves low reaction temperature and wide industrial application prospects , the effect of low temperature

Active Publication Date: 2022-02-11
CHANGSHU INSTITUTE OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0014] Although these methods are feasible and practical, the price of palladium metal is too expensive; although the nickel catalyst is cheap, it is not suitable for industrial production when it uses DIBAL; Long-chain and short-chain olefin protecting groups have not been tried

Method used

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  • Nickel Catalytic Removal of Alkene Protecting Groups
  • Nickel Catalytic Removal of Alkene Protecting Groups
  • Nickel Catalytic Removal of Alkene Protecting Groups

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0107]

[0108] Take a 10ml dry Schlenk reaction tube, weigh 0.3mmol of B in sequence 2 Pin 2 (pinacol borate), 0.01mmolNiCl 2 (DME), 0.02mmol of organic ligand L4, 0.2mmol of raw material (I) and 0.4mmol of lithium tert-butoxide, double pipe operation three times; sequentially inject DMA (N,N-dimethylacetamide) 2ml, water 50ul , 0.1 mmol methanol; then vigorously stirred at 30°C for 24h.

[0109] After the reaction, add 1M hydrochloric acid to adjust the pH to 2, add 20ml of water, extract with 20ml of ethyl acetate three times, collect the organic phase, wash with saturated saline, dry with anhydrous magnesium sulfate, concentrate, and then use 200 mesh Silica gel column chromatography to obtain the product (II) with a yield of 96%.

[0110] 1H NMR (400MHz, CDCl3) δ7.57(d, J=7.4Hz, 2H), 7.51(d, J=8.1Hz, 2H), 7.45(t, J=7.3Hz, 2H), 7.35(d, J = 7.1 Hz, 1H), 6.94 (d, J = 8.1 Hz, 2H), 4.95 (s, 1H). 13C NMR (101 MHz, CDCl3) δ 155.08, 140.78, 134.08, 128.74, 128.41, 126.74, ...

Embodiment 2

[0112]

[0113] Take a 10ml dry Schlenk reaction tube, weigh 0.3mmol of B in sequence 2 Pin 2 , 0.01mmol NiCl 2 (DME), 0.02mmol of organic ligand L4, and 0.4mmol of lithium tert-butoxide, double row tube operation three times; sequentially inject DMA2ml, water 50ul, 0.1mmol of methanol and 0.2mmol of raw material (I); then vigorously Stir for 24h.

[0114] After the reaction, add 1M hydrochloric acid to adjust the pH to 2, add 20ml of water, extract with 20ml of ethyl acetate three times, collect the organic phase, wash with saturated saline, dry with anhydrous magnesium sulfate, concentrate, and then use 200 mesh Silica gel column chromatography to obtain the product (II) with a yield of 92%.

[0115] 1 HNMR (400MHz, CDCl 3 )δ7.19(t, J=8.1Hz, 1H), 6.96(d, J=8.0Hz, 1H), 6.89(s, 1H), 6.75(dd, J=7.2, 0.9Hz, 1H), 5.35( s, 1H). 13 CNMR (101MHz, CDCl 3)δ 155.99, 135.00, 130.62, 121.36, 116.00, 113.87. see image 3 as well as Figure 4 , are respectively the proton nuc...

Embodiment 3

[0117]

[0118] Take a 10ml dry Schlenk reaction tube, weigh 0.3mmol of B in sequence 2 Pin 2 , 0.01mmolNiCl 2 (DME), 0.02mmol of organic ligand L4, and 0.4mmol of lithium tert-butoxide, operated three times in a double row tube; sequentially inject 2ml of DMA (N,N-dimethylacetamide), 50ul of water, 0.1mmol of methanol and 0.2 mmol starting material (I); then vigorously stirred at 30° C. for 24 h.

[0119] After the reaction, add 1M hydrochloric acid to adjust the pH to 2, add 20ml of water, extract with 20ml of ethyl acetate three times, collect the organic phase, wash with saturated saline, dry with anhydrous magnesium sulfate, concentrate, and then use 200 mesh Silica gel column chromatography to obtain the product (II) with a yield of 87%.

[0120] 1 HNMR (400MHz, CDCl 3 )δ7.16(t, J=8.0Hz, 1H), 6.54(d, J=7.8Hz, 1H), 6.47(d, J=7.9Hz, 2H), 5.65(s, 1H), 3.80(s, 3H). 13 CNMR (101MHz, CDCl 3 )δ160.80, 156.74, 130.32, 108.15, 106.60, 101.73, 55.38. See Figure 5 as w...

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Abstract

The invention relates to a method for nickel-catalyzed removal of olefin protecting groups, comprising: placing an olefin-containing compound in an organic solvent, in the presence of a catalyst, an organic ligand, pinacol diborate, alkali, alcohol and water The catalyst is a nickel-containing catalyst; after the reaction is finished, add an excess of 1M hydrochloric acid solution to adjust the pH to acidity, stir at room temperature until clarification, then extract with water and ethyl acetate, wash the organic phase with saturated brine, and then use Dry over sodium sulfate, concentrate, and separate by 200-300 mesh silica gel column chromatography to obtain alcohol or phenol-containing compounds. The invention uses common chemical reagents at a temperature of 30°C to efficiently remove a series of olefin primary alkyl halide protecting groups, and has good application prospects and wide industrialization potential in the field of organic synthesis.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and relates to a method for removing olefin protecting groups, in particular to a nickel-catalyzed method for removing olefin protecting groups. Background technique [0002] In the field of organic synthesis, primary alkyl halides (allyl bromide) terminated in alkenes are often used to protect phenols / alcohols, and the protective groups are removed after the reaction to obtain the corresponding products. [0003] At present, in the technical field of organic synthesis, the methods for de-terminating primary alkyl halides of olefins are mainly divided into non-transition metal catalyzed methods and transition metal catalyzed methods. Non-transition metal catalyzed methods mainly include: DDQ; NaBH 4 / I 2 ; MeSiCl / NaI; NiCl 2 / NaBH 4 Wait. Transition metal catalysis mainly includes: Pd; NiCl 2 (dppp), etc., here we focus on several methods of the current transition metal catalysis. [0004]...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C37/50C07C39/15C07C39/367C07C41/26C07C43/23C07C253/30C07C255/53C07C67/30C07C69/84C07C47/565C07C39/225B01J31/22
CPCC07C37/50C07C41/26C07C253/30C07C67/30C07C45/61B01J31/1815B01J2531/847B01J2231/00C07C39/15C07C39/367C07C43/23C07C255/53C07C69/84C07C47/565C07C39/225Y02P20/55
Inventor 易钧吴问刚唐晓艳殷文宇马运声袁荣鑫
Owner CHANGSHU INSTITUTE OF TECHNOLOGY
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